Pesticides

ABSTRACT

Compounds of formula (I) or pesticidally acceptable salts thereof, compositions containing them and methods of use.

This application is a divisional of Application Ser. No. 10/060,229,filed Feb. 1, 2002 now U.S. Pat. No. 6,500,848, which is a divisional ofApplication Ser. No. 09/930,946, filed Aug. 17, 2001, now U.S. Pat. No.6,376,520, which is a divisional of Application Ser. No. 09/440,850,filed Nov. 16, 1999, now U.S. Pat. No. 6,277,848, which is a divisionalof Application Ser. No. 08/946,648, filed Oct. 7, 1997, now U.S. Pat.No. 6,107,314, all of which are incorporated by reference.

The present invention relates to novel pesticides and compositionscontaining them. The invention particularly pertains to compositions ofsaid compounds and methods and use of said compounds for the control ofarthropod, nematode, helminth or protozoan pests, in particular to theapplication of said compounds or compositions in agricultural methods ofuse, particularly as pesticides, for controlling arthropods, especiallyinsects by systemic action.

The control of insects, nematodes or helminths by means of an activeingredient having a 1-arylpyrazole group therein has been described insuch patent applications such as International Patent Publication No. WO93/06089, WO 94/21606, WO 92/13451 and WO 87/03781 as well as inEuropean Patent Publication Numbers 0295117, 659745, 679650, 201852 and412849, German Patent No. DE19511269 and U.S. Pat. No. 5,232,940.

It is an object of the present invention to provide new pesticidalcompounds of the 1-arylpyrazole family together with processes for theirpreparation.

A second object of the present invention is to provide pesticidalcompositions and pesticidal methods of use of the pesticidal pyrazolecompounds against arthropods, especially insects, plant nematodes, orhelminth or protozoan pests, particularly in agricultural orhorticultural crops, forestry, veterinary medicine or livestockhusbandry, or in public health.

A third object of the present invention is to provide very activecompounds, with broad spectrum pesticidal activity, as well as compoundswith selective special activity, e.g., aphicidal, miticidal, foliarinsecticidal, soil insecticidal and nematicidal, systemic, antifeedingor pesticidal activity via seed treatment.

A fourth object of the present invention is to provide compounds withsubstantially enhanced and more rapid activity, especially againstinsects and more particularly insects in their larval stages.

A fifth object of the present invention is to provide compounds withgreatly improved (greater and faster) penetration into pest species whentopically applied and thus provide enhanced movement of the compounds tothe pesticidal site(s) of action within the pest.

Another object of the present invention is to provide compounds withhigh activity and improved safety to the user and the environment.

These and other objects of the invention shall become readily apparentfrom the detailed description of the present invention.

These objects are met in whole or in part by the instant invention.

The instant invention provides arylpyrazoles of formula (I):

wherein:

A is selected from:

X is —O—, or —NR₁₇;

R₁ is hydrogen, substituted or unsubstituted alkyl or a lone pair ofelectrons;

R₂ is —S(O)_(n)R₁₈ or R₁₉;

R₃ is hydrogen, halogen, —C(O)R₂₀, —S(O)_(p)R₂₁, alkyl, haloalkyl,—OR₂₂, —N═C(R₂₃)(R₂₄), alkenyl, —NR₂₅R₂₆, 1H-pyrrol-1-yl,1H-pyrazol-1-yl, or —CH═NOH;

R₄, R₅ and R₇ are independently selected from hydrogen, halogen oralkyl;

R₆ is halogen, haloalkyl, haloalkoxy, —S(O)_(q)R₂₇ or SF₅;

R₈ and R₉ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl, —OR₂₈, —NR₂₉R₃₀and —S(O)_(m)R₃₁, —C(O)R₃₂, cyano or nitro; or

R₈ and R₉, together with carbon atoms to which they are attached mayform a divalent alkylene radical which may be interrupted by one or moreheteroatoms preferably selected from oxygen, nitrogen and sulfur;

R₁₀, R₁₁, R₁₂ and R₁₃ are independently selected from hydrogen, hydroxy,C(O)R₃₂, alkyl and haloalkyl; or R₁₀ and R₁₁ can together form acarbonyl radical; or R₁₂ and R₁₃ can together form a carbonyl radical;

R₁₄ and R₁₅ are independently selected from R₈; or R₁₄ and R₁₅ cantogether with the carbons to which they are attached a cyclic divalentalkylene radical which may be interrupted by one or more heteroatomspreferably selected from oxygen, nitrogen and sulfur;

R₁₆ is alkoxy, alkyl or substituted or unsubstituted amino;

Y is oxygen or sulfur;

R₁₇ is hydrogen, substituted or unsubstituted alkyl or a lone pair ofelectrons;

R₁₈ is alkyl, alkenyl, alkynyl, or C₃-C₆ cycloalkyl, each of which isoptionally substituted by one or more halogen;

R₁₉ is alkyl or haloalkyl;

R₂₀ is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy;

R₂₁ is alkyl haloalkyl, or aryl;

R₂₂ and R₂₃ are independently selected from hydrogen, alkyl andhaloalkyl;

R₂₄ is alkyl, haloalkyl, alkoxy or phenyl each of which is optionallysubstituted by one or more groups selected from hydroxy, halogen,alkoxy, —CN, alkyl, —S(O)_(r)-alkyl;

R₂₅ and R₂₆ are independently selected from hydrogen, NH₂, —S(O)_(r)R₃₄,—C(O)R₃₅, substituted or unsubstituted alkyl, substituted orunsubstituted alkenyl and alkynyl; or R₂₅ and R₂₆ may form together adivalent alkylene radical which may be interrupted by one or moreheteroatoms, preferably selected from oxygen, nitrogen and sulfur;

R₂₇ is haloalkyl;

R₂₈ is hydrogen, substituted or unsubstituted alkyl, —C(O)R₃₃, orsubstituted or unsubstituted aryl;

R₂₉ and R₃₀ are independently selected from hydrogen, substituted orunsubstituted alkyl; or R₂₉ and R₃₀ may with the nitrogen to which theyare attached form a divalent alkylene radical which may be interruptedby one or more heteroatoms;

R₃₁ is alkyl haloalkyl or aryl;

R₃₂ and R₃₃ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl, hydroxy, alkoxy,and substituted or unsubstituted amino;

R₃₄ is substituted or unsubstituted alkyl;

R₃₅ is hydrogen, alkyl, haloalkyl, aryl; alkenyl; —OR₃₆, —SR₃₇, or—NR₃₈R₃₉;

R₃₆ and R₃₇ are independently selected from hydrogen, alkyl haloalkyland aryl;

R₃₈ and R₃₉ are independently selected from hydrogen, alkyl haloalkyland aryl;

m, n, p, q, r, s, and t independently represent zero, one or two;

M is C-halo, C—CH₃, C—CH₂F, C—CH₂Cl, C—NO₂, or N;

or a pesticidally acceptable salt thereof;

provided that:

when A is (G4) and X is —O—, R₁ is a lone pair of electrons and thenitrogen to which

R₁ is attached forms a double bond with the central carbon of the G4group;

when A is (G5), X is NR₁₇ and R₁ and R₁₇ represent lone pairs ofelectrons;

when A is (G2), R₁₀ and R₁₁ are not simultaneously hydroxy;

when A is (G2), R₁₂ and R₁₃ are not simultaneously hydroxy.

By the term “pesticidally acceptable salts” is meant salts the anionsand cations of which are known and accepted in the art for the formationof pesticidally acceptable salts. Preferably such salts are watersoluble. Suitable acid addition salts formed from compounds of formula(I) containing an amine group, include salts with inorganic acids forexample hydrochlorides, phosphates, sulfates and nitrates, and saltswith organic acids for example acetates. Suitable salts with basesformed by compounds of formula (I) include alkali metal (for examplesodium or potassium) salts, ammonium salts and organic amine (forexample diethanolamine or morpholine) salts.

Preferably by the term “substituted” is meant substituted by one or moreof the following substituents: halogen, hydroxy, cyano, carboxyl, —C(O)alkyl, —C(O) O-alkyl, —C(O)NH₂, —C(O)NH alkyl, —C(O)N (alkyl)₂, aryl,nitro, azido, amino, alkylamino, dialkylamino, alkylsulfenyl,alkylsulfinyl, alkylsulfonyl, aryloxy, arylthio, alkylcarbonyl, amino,alkylcarbonyloxy, or aryloxycarbonyl.

Unless otherwise specified, alkyl groups and moieties including themhave from one to six, preferably one to four, carbon atoms, alkenylgroups have from two to six, preferably two to four, carbon atoms, andalkynyl groups have from three to six, preferably three to four carbonatoms. By the term “aryl” is meant mono or polycyclic aromatic moieties,preferably including phenyl, pyridyl, pyrimidinyl, furyl and naphthylgroups. The term “halo” before the name of a radical means that thisradical is partially or completely halogenated, that is to say,substituted by F, Cl, Br or I, in any combination, preferably F or Cl.The term “halogen” means F, Cl, Br or I. It shall be understood that therings formed by the divalent alkylene radicals which includes the atomsto which they are attached are generally 5, 6 and 7 membered rings.

A preferred class of a compound of formula (I) are those with one ormore of the following features:

A is (G1), (G3) or (G4);

R₁ is hydrogen or a lone pair of electrons;

R₈ and R₉ are selected from alkyl, haloalkyl and hydrogen; or

Y is oxygen.

A very preferred class of compounds of formula (I) is that wherein:

A is (G3);

Y is oxygen or sulfur;

R₁ is hydrogen or alkyl;

R₂ is —S(O)_(n)R₁₈;

R₃ is NR₂₅R₂₆;

R₄ is halogen;

R₅ and R₇ are hydrogen;

R₆ is haloalkyl;

R₁₈ is alkyl; and

R₂₅ and R₂₆ are independently selected from hydrogen and alkyl.

R₂₅ and R₂₅ are independently selected from hydrogen or alkyl.

Another very preferred class of compounds of formula (I) is thatwherein:

A is (G1);

R₈ and R₉ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl and —C(O)R₃₂;

R₁ is hydrogen;

R₂ is —S(O)_(n)R₁₈;

R₃ is NR₂₅R₂₆;

R₄ is halogen;

R₅ and R₇ are hydrogen;

R₆ is haloalkyl;

R₁₈ is alkyl;

R₂₅ and R₂₆ are independently selected from hydrogen and alkyl; and

R₃₂ is alkyl, haloalkyl, alkoxy, or hydroxy.

Another very preferred class of compounds according to the instantinvention is that wherein:

A is (G4);

R₈ is alkyl or haloalkyl, preferably methyl or halomethyl;

X is —NH— or O;

R₁ is a lone pair of electrons;

R₂ is —S(O)_(n)R₁₈;

R₃ is NR₂₅R₂₆;

R₄ is halogen;

R₅ and R₇ are hydrogen;

R₆ is haloalkyl;

R₁₈ is alkyl; and

R₂₅ and R₂₆ are independently selected from hydrogen and alkyl.

Another very preferred class of compounds of formula (I) is thatwherein:

A is (G2);

R₁ is H or alkyl;

X is —NH— or O;

R₁₀, R₁₁, R₁₂ and R₁₃ are selected from hydrogen, —OH, and —C(O)R₃₂;

R₂ is —S(O)_(n)R₁₈;

R₃ is NR₂₅R₂₆;

R₄ is halogen;

R₅ and R₇ are hydrogen;

R₆ is haloalkyl;

R₁₈ is alkyl;

R₂₅ and R₂₆ are independently selected from hydrogen and alkyl; and

R₃₂ is alkoxy or amino.

Preferred aryl groups comprising the R₄ to R₇ and M radicals in formula(I) are: 2,6-dichloro-4-trifluoromethylphenyl;2,6-dichloro-4-trifluoromethoxyphenyl;2-bromo-6-chloro-4-trifluoromethylphenyl;2-bromo-6-chloro-4-trifluoromethoxyphenyl;2,6-difluoro-4-trifluoromethylphenyl; 2-chloro-4-trifluoromethylphenyl;3-chloro-5-trifluoromethyl-2-pyridinyl;3-chloro-5-trifluoromethoxy-2-pyridinyl;2-bromo-6-fluoro-4-difluoromethylphenyl;2-chloro-6-fluoro-4-trifluoromethylphenyl;2,6-dibromo-4-trifluoromethylphenyl;2,6-dibromo-4-trifluoromethoxyphenyl; and2,6-dichloro-4-pentafluorothiophenyl.

Among the compounds of general formula (I) are the followingparticularly preferred compounds which provide particularly usefulcontrol of insect species by systemic action. The compound numbers arefor reference only.

Wherein R₃ is NH₂; R₄ is C—Cl, M is C—Cl, R₅═R₆═H; R₆ is CF₃ and

1) A is G4, X is O, R₂ is SOCH₃, R₈ is CF₃: m.p. about 159° C.;

2) A is G4, X is O, R₂ is SOCH₃, R₈ is CCl₃: m.p. about 98° C.;

3) A is G4, X is O, R₂ is SOEt, R₈ is CF₃: m.p. about 155° C.;

4) A is G4, X is O, R₂ is SOCH₃, R₈ is CF₃: m.p. about 156° C.;

5) A is G4, X is O, R₂ is SCH₃, R₈ is CH₃: m.p. about 75° C.;

6) A is G4, X is NH, R₂ is SOCF₃, R₈ is CF₃: m.p. about 81° C.;

7) A is G1, X is NH, R₂ is SOCH₃, R₉ is H, R₈ is —C(CH₃)₂CH₂OH: m.p.about 207° C.;

8) A is G1, X is NH, R₂ is SOCH₃, R₉ is H, R₈ is CF₃: m.p. about 109°C.;

9) A is G1, X is NH, R₂ is SOCH₃, R₉ is H, R₈ is 2-furanyl: m.p. about120° C.;

10) A is G1, X is NH, R₂ is SOCH₃, R₉ is H, R₈ is (3-methyl)phenyl: m.p.about 120° C.;

11) A is G1, X is NH, R₂ is SOCH₃, R₉ is H, R₈ is —COOH: (oil);

12) A is G1, X is NH, R₂ is SOCH₃, R₉ is H, R₈ is phenyl: (oil);

13) A is G1, X is —O—, R₂ is SOCH₃, R₉ is H, R₈ is CH₃: m.p. about 204°C.;

14) A is G1, X is —O—, R₂ is SOCH₃, R₉ is H, R₈ is phenyl: m.p. about118° C.;

15) A is G7, X is O, R₂ is SOCH₃, R₉ is H, R₈ is ethyl: m.p. about 111°C.;

16) A is G3, Y is O, X is NH, R₁ is H, R₂ is SOCH₃: m.p. about 207° C.;

17) A is G3, Y is O, X is NH, R₁ is isopropyl, R₂ is SOCH₃: (oil);

18) A is G3, Y is S, X is NH, R₁ is H, R₂ is SOCH₃, (oil);

19) A is G2, X is O, R₁ is H, R₂ is SOCH₃, R₁₀ is methyl, R₁₁ and R₁₂are hydroxy, R₁₃ is H: m.p. about 194° C.;

20) A is G2, X is O, R₁ is H, R₂ is SOCH₃, R₁₀ is H, R₁₁ and R₁₂ arehydroxy, R₁₃ is H: m.p. 207° C.;

21) A is G8, X is NH, R₁ is H, R₂ is SOCH₃, R₁₀ is H, R₁₁ and R₁₂ are—COOEt, R₁₃ is H: m.p. about 95° C.;

22) A is G8, X is NH, R₁ is H, R₂ is SOCH₃, R₁₀ is H, R₁₁ and R₁₂ are—CONH₂, R₁₃ is H; and

23) A is G5, X is NR₁₇, R₁ and R₁₇ are lone pairs of electrons, R₁₄ andR₁₅ are H, R₂ is SOCH₃: m.p. about 160° C.

According to a further feature of the invention, compounds of generalformula (I) are prepared from compounds of formula (II):

by reaction with:

a) in the case of A=G1, an aldehyde or ketone of general formulaR₈C(O)R₉ generally in the presence of an acid such as hydrogen chlorideand optionally in the presence of a water removal means, the reactionbeing generally effected in a solvent such as methylene chloride and atthe reflux temperature of the solvent;

b) in the case of A=G2, an aldehyde or ketone of general formulaR₁₀C(O)C(O), R₁₃ wherein R₁₀ and R₁₃ are independently selected fromhydrogen or alkyl, generally in the presence of an acid such as hydrogenchloride and optionally in the presence of a water removal means, thereaction being generally effected in a solvent such as methylenechloride and at the reflux temperature of the solvent or with a compoundof general formula R₁₀R₁₁CLCLR₁₂R₁₃; wherein ‘L and L’ are leavinggroups such as halogen; and wherein R₁₀, R₁₁, R₁₂ and R₁₃ are nothydroxy, generally in the presence of a base and optionally in asolvent; or with a compound R₃₂C(O)CC(O)R₃₂ in the optionally in thepresence of a base;

c) in the case of A=G3, phosgene or thiophosgene, carbonyldiimidazole,or other phosgene equivalents known to persons skilled in the art ofchemical synthesis, generally in the presence of a base such as pyridineor an alkali metal carbonate in a solvent such as methylene chloride andat a temperature generally from −100° to 100° C.;

d) in the case of A=G4, and R₁ is H, an orthoester, in the presence ofan acid catalyst such as para-toluene sulfonic acid, the reactiongenerally being effected in a solvent which can be an alcohol (such asethanol) and generally at the reflux temperature of the solvent;

e) in the case of A=G5, wherein X is NH and R₁₇ is H, a dicarbonylcompound of formula R₁₄C(O)C(O)R₁₅ in the presence of an acid catalystsuch as hydrogen chloride optional water removal means and optionally ina solvent, the temperature of the reaction generally being at the refluxtemperature of the solvent;

f) in the cases of A=G6 and G7 with phosphorylating sulfenylating,sulfinylating or sulfonylating reagents such as ethyldichlorophosphate,ethyldichlorothiophosphate, thionylchloride, sulfonyl chloride, sulfurmonochloride and the like; and generally in the presence of a base suchas methylamine or sodium hydrogen carbonate and optionally in thepresence of a solvent.

According to a further feature of the present invention compounds ofgeneral formula (II) in which R₁ is H may be prepared by the reaction ofa compound of formula (III):

with a compound of formula (IV)

H₂NX—H  (IV)

in which X is defined above. The reaction is generally performed usingan acid salt of a compound of formula (IV), for example thehydrochloride salt, and in the presence of a base for example pyridineor an alkali metal carbonate (such as sodium carbonate) or an alkalimetal acetate (such as sodium acetate) or ammonium acetate in a solventsuch as methanol and/or water at a temperature from 0° C. to 100° C.

According to a further feature of the present invention compounds ofgeneral formula (II) wherein R₁ is H may be prepared by the reaction ofa compound of formula (V):

wherein R represents alkyl, with a compound of formula (IV). Thereaction is generally performed using an acid salt of a compound offormula (IV), for example the hydrochloride salt, and optionally in thepresence of a base (for example pyridine or an alkali metal carbonatesuch as sodium carbonate) or an alkali metal acetate (such as sodiumacetate or ammonium acetate) in a solvent such as methanol and/or waterand generally at a temperature from 0° C. to 100° C.

According to a further feature of the invention, compounds of formula(II) wherein R₁ is alkyl may be prepared from compounds of formula (II)wherein R₁ is H by alkylation, a process known to those skilled in theart of chemical synthesis.

The compounds of formula (III) wherein R₂, R₃, R₄, R₅, R₆ and M are theabove described substituents can be prepared by methods described in oneor more of the following: WO 94/21606, WO 93/06089, WO 87/03781, WO97/22593; European Patent Publications EP 0295117, EP 0511845, EP0403309, EP 0403300, EP 352944, EP 780378; U.S. Pat. Nos. 5,232,940,5,047,550, 4,918,085; German Patent Publication No. 19511269; or bymethods known to those skilled in the art.

The synthesis of high oxidation states of the compounds of formula (I),i.e., compounds in which m, n, p, q, r, and s are 1 or 2, can beachieved by oxidation of the corresponding compounds in which thosevariables are 0 or 1.

Intermediates of formula (III) may be prepared by known methods (see forexample the above listed references).

Certain compounds of formula (III) are novel and as such constitute afurther feature of the invention.

The following Examples 1 to 7 and Reference Examples 1 to 3 illustratedetailed methods of synthesis and their physical properties ofrepresentative pesticidal compounds of formula (I) according to theinvention.

EXAMPLE 1 Preparation of Compound 1

The mixture of Reference Compound 1 and trifluoroacetic anhydride (757mg) in dioxane (10 ml) was stirred at room temperature for 4 days. Themixture was evaporated and the residue purified by silica gelchromatography to provide 79 mg of Compound 1. The mass spectralanalysis of the compound gave M+H+494.

In similar manner, Compounds, 2, 3, 4, and 5 were prepared.

EXAMPLE 2 Preparation of Compound 6

Reference Compound 2 (0.50 g) trifluoroacetic anhydride (0.226 ml) andp-dioxane were placed in a 50 mL round-bottomed flask. The reactionmixture was stirred at room temperature over night. The solvent wasevaporated. The residue was washed with hexane and a precipitate slowlysolidified upon standing at room temperature to provide 0.50 g ofCompound 6, m.p. about 79-84° C., 85% yield.

EXAMPLE 3 Preparation of Compound 14

A mixture of Reference Compound 1 and benzaldehyde (731 μl) in aceticacid (4 ml) was stirred at room temperature overnight. The mixture wasevaporated and the residue purified by silica gel chromatography toprovide 540 mg of Compound 4, m.p. about 116-120° C.

In a similar manner Compounds 13 and 15 were prepared.

EXAMPLE 4 Preparation of Compound 19

The mixture of Reference Compound 1 (1.0 g) and pyruvic aldehyde (1.10ml) in acetic acid (4 ml) was stirred at room temperature for 4 days.The mixture was evaporated and the residue purified by silica gelchromatography to give 220 mg of Compound 19, m.p. about 116-120° C.

Compound 20 was prepared in a similar manner.

EXAMPLE 5 Preparation of Compound 7

The reaction mixture of Reference Compound 3 (0.61 g) and2,2-dimethyl-3-hydroxylpropionaldehyde (0.195 g) in ethanol (10 ml) washeated to reflux overnight. The solvent was removed and the residuepurified by silica gel chromatography to provide Compound 7 as a whitepowder (0.566 g), m.p. about 207° C.

In a similar manner Compounds 8, 9, 10, 11 and 12 were prepared.

EXAMPLE 6 Preparation of Compound 15

Reference Compound 3 (1.025 g) and 1,1′-carbonyldiimidazole (0.58 g)were dissolved in dry ether (10 ml) and dry THF (10 ml). The reactionmixture was stirred at room temperature under a nitrogen atmosphereovernight. Solvent was removed and the residue was re-dissolved in ethylacetate. The product was precipitated out with hexane. Thisprecipitation procedure was repeated once to afford Compound 16 as apale yellow powder (0.49 g), m.p. about 207° C.

In a similar manner Compounds 17 and 18 were prepared.

EXAMPLE 7 Preparation of Compound 23

A reaction mixture of Reference Compound 3 (0.65 g) and glyoxal (40% wt.Aqueous solution, 0.23 ml in ethanol (10 ml) was heated to reflux andstirred overnight. The solvent was evaporated and the residue waspurified by silica gel to provide Compound 23 as a white powder (0.63g), m.p. about 160° C.

EXAMPLE 8 Preparation of Compound 21

The reaction mixture of Reference Compound 3 (0.55 g) and diethylacetylenedicarboxylate (0.26 ml) in ethanol (10 ml) was stirred at roomtemperature for 3 days. The mixture was evaporated and the residuepurified by silica gel to provide Compound 21 (0.61 g), m.p. about 95°C.

Compound 22 was prepared by a similar process.

REFERENCE COMPOUND 1

To a suspension of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole(20 g) in methanol (120 ml) was added hydroxylamine hydrochloride (3.99g), followed by addition of triethylamine (8.0 ml). The mixture wasstirred at room temperature overnight then evaporated. The residue waspartitioned between water and ethyl acetate. The organic layer waswashed with water, followed by wash with brine. The organic layer wasdried over anhydrous sodium sulfate. The solution was concentrated byevaporation of solvent. A precipitate was formed and collected byfiltration. The solid was washed with small amount of ethyl acetate togive the desired5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsulfinyl-3[3-(1-amidoxime)]-pyrazole(16.1 g), m.p. 225-226° C.

REFERENCE COMPOUND 2

A mixture of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole(6.0 g) and hydrazine (3.5 g) in ethanol (12 ml ) was heated to 105° C.for 3.5 hr under a nitrogen atmosphere. The mixture was cooled to roomtemperature and stirred at room temperature overnight. The mixture wasevaporated. The yellow residue was washed with hexane and a precipitatewas formed. The precipitate was washed with more hexane. The residue wasdissolved in ethyl acetate and hexane and filtered through a filterpaper and allowed to recrystallize. The solid was filtered to provide5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinyl-3[3-(1-aminoamidine)]pyrazole(2.88 g) m. p. 170-171° C.

REFERENCE COMPOUND 3

A mixture of5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-1H-pyrazole(550 g) and anhydrous hydrazine (700 g) in absolute ethanol (1.55 L) wasstirred at ambient temperature for four hours. Water (6.5 L) was addedand the precipitate filtered and washed with water. After 12 hoursanother batch of precipitate was filtered. All solids were combined toprovide 568 g of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsulfinyl-3[3-(1-aminoamidine)]pyrazoleas a white solid, m.p. about 210° C.

MITICIDE, INSECTICIDE, APHICIDE, and NEMATICIDE USE

The following representative test procedures, using compounds of theinvention, were conducted to determine the pesticidal use and activityof compounds of the invention against: mites; certain insects, includingaphids, two species of caterpillar, a fly, and three species of beetlelarvae (one foliar feeding and two root feeding); and nematodes. Thespecific species tested were as follows:

GENUS, SPECIES COMMON NAME (ABBREVIATION) Tetranychus urticae twospottedspider mite TSM Aphis nasturtii buckthorn aphid BA Spodoptera eridaniasouthern armyworm SAW Epilachna varivestis Mexican bean beetle MBB Muscadomestica housefly HF Diabrotica u. southern corn rootworm SCRW howardiDiabrotica virgifera western corn rootworm WCRW Meloidogyne southernroot-knot nematode SRKN incognita Aphis gossypii cotton aphid CASchizaphis greenbug (aphid) GB graminum Heliothis virescens tobaccobudworm TBW

Formulations

The test compounds were formulated for use according to the followingmethods used for each of the test procedures.

For mite, aphid, southern armyworm, Mexican bean beetle, and tobaccobudworm tests, a solution or suspension was prepared by adding 10 mg ofthe test compound to a solution of 160 mg of dimethylformamide, 838 mgof acetone, 2 mg of a 3:1 ratio of Triton X-172: Triton X-152(respectively, mainly anionic and nonionic low foam emulsifiers whichare each anhydrous blends of alkylaryl polyether alcohols with organicsulfonates), and 98.99 g of water. The result was a concentration of 100ppm of the test compound.

For housefly tests, the formulation was initially prepared in a similarmanner to the above, but in 16.3 g of water with correspondingadjustment of other components, providing a 200 ppm concentration. Finaldilution with an equal volume of a 20% by weight aqueous solution ofsucrose provided a 100 ppm concentration of the test compound. Whennecessary, sonication was provided to insure complete dispersion.

For southern and western corn rootworm tests, a solution or suspensionwas prepared in the same manner as that used for the initial 200 ppmconcentration for housefly. Aliquots of this 200 ppm formulation werethen used by dilution with water according to the required testconcentration.

For southern root-knot nematode and systemic tests for southernarmyworm, cotton aphid, tobacco budworm and greenbug, a stock solutionor suspension was prepared by adding 15 mg of the test compound to 250mg of dimethylformamide, 1250 mg of acetone and 3 mg of the emulsifierblend referenced above. Water was then added to provide a test compoundconcentration of 150 ppm. When necessary, sonication was provided toinsure complete dispersion.

For tobacco budworm contact tests, a stock solution was prepared bydissolving the compound in acetone and then further diluted to providethe required serial dilution concentrations.

Test Procedures

The above formulated test compounds were then evaluated for theirpesticidal activity at the specified concentrations, in ppm (parts permillion) by weight, according to the following test procedures:

Twospotted spider mite: Leaves infested with adult and nymphal stages ofthe two-spotted spider mite, obtained from a stock culture were placedon the primary leaves of two bean plants growing in a 6 cm. peat pot. Asufficient number of mites (150-200) for testing were transferred to thefresh plants within a period of twenty-four hours. The potted plants(one pot per compound) were placed on a revolving turntable and sprayed,sufficient to wet the plants to runoff, with 100 ml of the 100 ppm testcompound formulation by use of a DeVilbiss spray gun set at 40 psig. airpressure. As an untreated control, 100 ml of thewater-acetone-DMF-emulsifier solution, containing no test compound, werealso sprayed on infested plants. A treated control with a commercialtechnical compound, either dicofol or hexythiazox, formulated in thesame manner, was tested as a standard. The sprayed plants were held forsix days, after which a mortality count of motile forms was made.

Twospotted spider mite (ovicide test): Eggs were obtained from adults ofthe twospotted spider mite from a stock culture. Heavily infested leavesfrom the stock culture were placed on uninfested bean plants. Femaleswere allowed to oviposit for a period of about 24 hours, after which theleaves of the plant were dipped into a solution of TEPP (tetraethyldiphosphate) in order to kill the motile forms and prevent additionalegg laying. This dipping procedure, which was repeated after the plantsdried, did not affect the viability of the eggs. The potted plants (onepot per compound) were placed on a revolving turntable and sprayed,sufficient to wet the plants to runoff, with 100 ml of the 100 ppm testcompound formulation by use of a DeVilbiss spray gun set at 40 psig. airpressure. As an untreated control, 100 ml of thewater-acetone-DMF-emulsifier solution, containing no test compound, werealso sprayed on infested plants. A treated control with a commercialtechnical compound, typically demeton, formulated in the same manner,was tested as a standard. The sprayed plants were held for seven days,after which a mortality count of egg forms was made along with notationson residual activity on hatched larvae.

Buckthorn or cotton aphid: Adult and nymphal stages of buckthorn orcotton aphid were reared on potted dwarf nasturtium or cotton plants,respectively. The potted plants (one pot per compound tested) infestedwith 100-150 aphids, were placed on a revolving turntable and sprayedwith 100 ml of the 100 ppm test compound formulation by use of aDeVilbiss spray gun set at 40 psig air pressure. As an untreatedcontrol, 100 ml of a water-acetone-DMF-emulsifier solution, containingno test compound, were also sprayed on infested plants. A treatedcontrol with a commercial technical compound, malathion or cyhalothrin,formulated in the same manner, was tested as a standard. After spraying,the pots were stored for one day on buckthorn aphid or three days forcotton aphid, after which the dead aphids were counted.

Southern armyworm: Potted bean plants, were placed on a revolvingturntable and sprayed with 100 ml of the 100 ppm test compoundformulation by use of a DeVilbiss spray gun set at 40 psig air pressure.As an untreated control, 100 ml of a water-acetone-DMF-emulsifiersolution, containing no test compound, were also sprayed on plants. Atreated control with a commercial technical compound, eithercypermethrin or sulprofos, formulated in the same manner, was tested asa standard. When dry, the leaves were placed in plastic cups lined withmoistened filter paper. Five randomly selected second instar southernarmyworm larvae were introduced into each cup which was closed and heldfor five days. Larvae which were unable to move the length of the body,even upon stimulation by prodding, were considered dead.

Tobacco budworm: Potted cotton plants were placed on a revolvingturntable and sprayed with 100 ml of the 100 ppm test compoundformulation by use of a DeVilbiss spray gun set at 40 psig air pressure.As an untreated control, 100 ml of a water-acetone-DMF-emulsifiersolution, containing no test compound, were also sprayed on plants. Atreated control with a commercial technical compound, eithercypermethrin or sulprofos, formulated in the same manner, was tested asa standard. When dry, the leaves were placed in plastic dishescontaining a piece of filter paper and a moistened dental wick. Onerandomly selected second instar tobacco budworm larva was thenintroduced into each cup which was closed and held for five days. Larvaeunable to move the length of their body, even upon stimulation byprodding, were considered dead.

Mexican bean beetle: Potted bean plants were placed on a revolvingturntable and sprayed with 100 ml of the 100 ppm test compoundformulation, sufficient to wet the plants to runoff, by use of aDeVilbiss spray gun set at 40 psig air pressure. As an untreatedcontrol, 100 ml of a water-acetone-DMF-emulsifier solution, containingno test compound, were also sprayed on plants. A treated control with acommercial technical compound, either cypermethrin or sulprofos,formulated in the same manner, was tested as a standard. When dry, theleaves were placed in plastic cups lined with moistened filter paper.Five randomly selected second instar Mexican bean beetle larvae wereintroduced into each cup which was closed and held for five days. Larvaewhich were unable to move the length of the body, even upon stimulationby prodding, were considered dead.

House fly: Four to six day old adult house flies were reared accordingto the specifications of the Chemical Specialties ManufacturingAssociation (Blue Book, McNair-Dorland Co., N.Y. 1954; pages 243-244,261) under controlled conditions. The flies were immobilized byanesthetizing with carbon dioxide and twenty five immobilizedindividuals, males and females, were transferred to a cage consisting ofa standard food strainer and a wrapping-paper-covered surface. Ten ml ofthe 100 ppm test compound formulation were added to a souffle cupcontaining an absorbent cotton pad. As an untreated control, 10 ml of awater-acetone-DMF-emulsifier-sucrose solution, containing no testcompound, were applied in a similar manner. A treated control with acommercial technical compound, malathion, formulated in the same manner,was tested as a standard. The bait cup was introduced inside the foodstrainer prior to admitting the anesthetized flies. After 24 hours,flies which showed no sign of movement on stimulation were considereddead.

Southern or western corn rootworm: Into a jar containing 60 g of sandyloam soil was added 1.5 ml of an aqueous formulation consisting of analiquot of the 200 ppm test compound formulation, diluted with water asappropriate for the final soil concentration of the test compound, 3.2ml of water and five pregerminated corn seedlings. The jar was shakenthoroughly to obtain an even distribution of the test formulation.Following this, twenty corn rootworm eggs (or optionally ten firstinstar larvae in the case of WCRW) were placed into a cavity, which wasmade in the soil. Vermiculite (1 ml), used optionally in the case ofWCRW tests, and water (1.7 ml) were then added to this cavity. In asimilar manner, an untreated control was prepared by application of thesame size aliquot of a water-acetone-DMF-emulsifier solution, containingno test compound. Additionally, a treated control with a commercialtechnical compound (selected typically from terbufos, fonofos, phorate,chlorpyrifos, carbofuran, isazophos, or ethoprop), formulated in thesame manner was used as needed as a test standard. After 7 days, theliving rootworm larvae were counted using a well known “Berlese” funnelextraction method.

Southern root-knot nematode: Infected roots of tomato plants, containingegg masses of southern root-knot nematode, were removed from a stockculture and cleaned of soil by shaking and washing with tap water. Thenematode eggs were separated from the root tissue and rinsed with water.Samples of the egg suspension were placed on a fine screen over areceiving bowl, in which the water level was adjusted to be in contactwith the screen. From the bowl, juveniles were collected on a finescreen. The bottom of a cone-shaped container was plugged with coarsevermiculite and then filled to within 1.5 cm of the top with about a 200ml volume of pasteurized soil. Then into a hole made in the center ofthe soil in the cone was pipetted an aliquot of the 150 ppm testcompound formulation. A treated control with a commerical technicalcompound, fenamifos, formulated in a similar manner, was tested as astandard. As an untreated control, an aliquot of awater-acetone-DMF-emulsifier solution, containing no test compound, wasapplied in a similar manner. Immediately after treatment of the soilwith the test compound there were added to the top of each cone 1000second stage juvenile southern root-knot nematodes. After 3 days, asingle healthy tomato seedling was then transplanted into the cone. Thecone, containing the infested soil and tomato seedling, was kept in thegreenhouse for 3 weeks. At the termination of the test, roots of thetomato seedling were removed from the cone and evaluated for galling ona rating scale relative to the untreated control as follows:

1—severe galling, equal to untreated control

3—light galling

4—very light galling

5—no galling, ie, complete control

These results were then converted to an ED₃ or ED₅ value (effective doseto provide a 3 or 5 gall rating).

Southern armyworm on tomato—systemic evaluation: This test was conductedin conjunction with the southern root-knot nematode evaluation(discussed below). The tomato plants, grown in the soil (at an initialcompound test screening rate of 6.6 ppm soil concentration or about 150ppm solution concentration) for nematode evaluation, were then utilizedfor evaluation of a compound's uptake via roots and subsequent systemictransport to the tomato foliage. At the termination of the nematodetest, 21 days after treatment, the tomato foliage was excised, placedinto a plastic container, and infested with second instar larvae ofsouthern armyworm. After about 5 days, the larvae were examined forpercent mortality.

Cotton aphid and tobacco budworm (on cotton) and greenbug and tobaccobudworm (on sorghum)—systemic evaluation: A 7.0 ml aliquot of the 150ppm nematode test solution was applied to deliver the equivalent of 10.0ppm soil concentration dose as a drench to 6 cm pots containing cottonand sorghum plants. The cotton plants were previously infested withcotton aphids about two days before treatment and greenbug one daybefore treatment. After holding the plants about three days, the plantswere rated for aphid activity. Again at six days, the plants were ratedfor aphid activity and the cotton aphids and greenbugs were counted andmortality was assessed. Portions of the cotton and sorghum foliage wereexcised, placed in separate plastic containers, and infested with secondinstar larvae of tobacco budworm. The potted plants were dipped insulfotepp to kill the remaining aphids and returned to the greenhousefor regrowth. Thirteen days after treatment, the remaining foliage wasexcised and fed to tobacco budworms. Mortality was assessed six daysafter infestation.

Cotton aphid and southern armyworm (on cotton) and greenbug and southernarmyworm (on sorghum)—systemic evaluation: A stock solution orsuspension was prepared to deliver 5 ml of a 20 ppm soil concentrationdose (and subsequent dilutions) as a drench to 6 cm pots containingcotton and sorghum plants. The cotton plants were previously infestedwith cotton aphids about two days before treatment and greenbug one daybefore treatment. After holding the plants about three days, the plantswere rated for aphid activity. Again at six days, the plants were ratedfor aphid activity and the cotton aphids and greenbugs were counted andmortality was assessed. Portions of the cotton and sorghum foliage wereexcised, placed in separate plastic containers, and infested with secondinstar larvae of southern armyworms. The potted plants were dipped insulfotepp to kill the remaining aphids and returned to the greenhousefor regrowth. Thirteen days after treatment the remaining foliage wasexcised and fed to southern armyworm. Mortality was assessed six daysafter infestation.

Cotton aphid and southern armyworm (on cotton and oats)—seed treatmentevaluation: Technical material was applied to the seed of oats andcotton by placing the compound and the seed in an appropriate sized jarand rolling the jar on a ball mill. Assay of the material applied to theseed was by weight. Seed was then planted. When germinated and emerged,the plants were infested at the appropriate intervals with host insects.Mortality was assessed on those insects.

Tobacco budworm—contact evaluation: The following topical applicationmethod provides an assessment of contact toxicity of a compound totobacco budworm larvae. The test compound solution at sequentialtwo-fold dilution concentrations from 10 down to 0.16 μg/μl was appliedby a microinjector in replicated 1 μl portions to the dorsum ofapproximately 20 mg tobacco budworm larvae. This is equivalent toapplied doses of 500 down to 8 μg/g body weight. An acetone treatedcontrol, without any test compounds, was also applied. A treated controlwith a commercial technical compound, cypermethrin or thiodicarb, alsoin acetone was used as a standard. The treated larvae were placed,individually, in separate plastic petri dishes containing an untreatedcotton leaf and a moist dental wick. The treated larvae were maintainedat about 27° C. and 50% relative humidity. The percent mortality wasrated 1 and 4 days after treatment.

All of the Compound Numbers 1 to 23 of the invention showed insecticidalactivity in one or more of the above evaluation methods, withparticularly good activity in the systemic tests.

METHODS AND COMPOSITIONS

The present invention provides a method for the systemic control ofarthropods at a locus, especially some insects or mites which feed onthe above ground portions of plants. Control of such foliar pests may beprovided by direct foliar application or by application by for examplesoil spray or granule application to the plant roots or plant seeds withsubsequent systemic translocation to the above ground portions of theplants. Such systemic activity includes the control of insects whichreside not only at the point of application but at a remote part of theplant for example by translocation from one side of a leaf to the otheror from a treated leaf to an untreated leaf. Examples of the classes ofinsect pests which may be systemically controlled by the arylpyrazolesof the invention include the Homoptera order (piercing-sucking),Hemiptera order (piercing-sucking), and Thysanoptera order. Theinvention is especially appropriate for aphids and thrips.

As is evident from the foregoing pesticidal uses, the present inventionprovides pesticidally active arylpyrazoles and methods of use of saidarylpyrazoles for the control of a number of pest species whichincludes: arthropods, especially insects or mites; plant nematodes; orhelminth or protozoan pests. The arylpyrazoles of formula (I) orpesticidally acceptable salts thereof thus are advantageously employedin practical uses, for example, in agricultural or horticultural crops,forestry, veterinary medicine or livestock husbandry, or in publichealth. From this point forward, whenever the term “arylpyrazoles offormula (I)” is used this term embraces arylpyrazoles of formula (I) andtheir pesticidally acceptable salts. The term “arylpyrazole of formula(I)” embraces a arylpyrazole of formula (I) and a pesticidallyacceptable salt thereof.

The present invention therefore provides a method of control of pests ata locus which comprises the treatment of the locus (e.g., by applicationor administration) with an effective amount of a arylpyrazole of formula(I) or a pesticidally acceptable salt thereof, wherein the substituentgroups are as hereinbefore defined. The locus includes, for example, thepest itself or the place (plant, animal, field, structure, premises,forest, orchard, waterway, soil, plant or animal product, or the like)where the pest resides or feeds.

The arylpyrazoles of this invention may in addition be used to controlsoil insects, such as corn rootworm, termites (especially for protectionof structures), root maggots, wireworms, root weevils, stalkborers,cutworms, root aphids, or grubs. They may also be used to provideactivity against plant pathogenic nematodes, such as root-knot, cyst,dagger, lesion, or stem or bulb nematodes, or against mites. For thecontrol of soil pests, for example corn rootworm, the arylpyrazoles areadvantageously applied to or incorporated at an effective rate into thesoil in which crops are planted or to be planted or to the seeds orgrowing plant roots.

In the area of public health, the arylpyrazoles are especially useful inthe control of many insects, especially filth flies or other Dipteranpests, such as houseflies, stableflies, soldierflies, hornflies,deerflies, horseflies, midges, punkies, blackflies, or mosquitoes.

Arylpyrazoles of the invention may be used in the following applicationsand on the following pests including arthropods, especially insects ormites, nematodes, or helminth or protozoan pests:

In the protection of stored products, for example cereals, includinggrain or flour, groundnuts, animal feedstuffs, timber or householdgoods, e.g. carpets and textiles, arylpyrazoles of the invention areuseful against attack by arthropods, more especially beetles, includingweevils, moths or mites, for example Ephestia spp. (flour moths),Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles),Sitophilus spp. (grain weevils) or Acarus spp. (mites).

In the control of cockroaches, ants or termites or similar arthropodpests in infested domestic or industrial premises or in the control ofmosquito larvae in waterways, wells, reservoirs or other running orstanding water.

For the treatment of foundations, structures or soil in the preventionof the attack on building by termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

In agriculture against adults, larvae and eggs of Lepidoptera(butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens(tobacco budworm), Heliothis armigera and Heliothis zea. Against adultsand larvae of Coleoptera (beetles) e.g. Anthonomus spp. e.g. grandis(cotton boll weevil), Leptinotarsa decemlineata (Colorado potatobeetle), Diabrotica spp. (corn rootworms). Against Heteroptera(Hemiptera and Homoptera) e.g. Psylla spp., Bemisia spp., Trialeurodesspp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp.,Nephotettix spp. (rice leaf hoppers), Nilaparvata spp.

Against Diptera e.g. Musca spp. Against Thysanoptera such as Thripstabaci. Against Orthoptera such as Locusta and Schistocerca spp.,(locusts and crickets) e.g. Gryllus spp., and Acheta spp. for example,Blatta orientalis, Periplaneta americana, Blatella germanica, Locustamigratoria migratorioides, and Schistocerca gregaria. Against Collembolae.g. Periplaneta spp. and Blattela spp. (roaches). Against Isoptera e.g.Coptotermes spp. (termites).

Against arthropods of agricultural significance such as Acari (mites)e.g. Tetranychus spp., and Panonychus spp.

Against nematodes which attack plants or trees of importance toagriculture, forestry or horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants. Forexample root-knot nematodes such as Meloidogyne spp. (e.g. M.incognita).

In the field of veterinary medicine or livestock husbandry or in themaintenance of public health against arthropods, helminths or protozoawhich are parasitic internally or externally upon vertebrates,particularly warm-blooded vertebrates, for example domestic animals,e.g. cattle, sheep, goats, equines, swine, poultry, dogs or cats, forexample Acarina, including ticks (e.g. Ixodes spp., Boophilus spp. e.g.Boophilus microplus, Rhipicephalus spp. e.g. Rhipicephalusappendiculatus Ornithodorus spp. (e.g. Ornithodorus moubata) and mites(e.g. Damalinia spp.); Diptera (e.g. Aedes spp., Anopheles spp., Muscaspp., Hypoderma spp.); Hemiptera; Dictyoptera (e.g. Periplaneta spp.,Blatella spp.); Hymenoptera; for example against infections of thegastro-intestinal tract caused by parasitic nematode worms, for examplemembers of the family Trichostrongylidae; in the control and treatmentof protozoal diseases caused by, for example, Eimeria spp. e.g.Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp.,Trichomonadidae spp., Toxoplasma spp. and Theileria spp.

In practical use for the control of arthropods, especially insects ormites, or nematode pests of plants, a method, for example, comprisesapplying to the plants or to the medium in which they grow an effectiveamount of a arylpyrazole of the invention. For such a method, the activearylpyrazole is generally applied to the locus in which the arthropod ornematode infestation is to be controlled at an effective rate in therange of about 5 g to about 1 kg of the active arylpyrazole per hectareof locus treated. Under ideal conditions, depending on the pest to becontrolled, a lower rate may offer adequate protection. On the otherhand, adverse weather conditions, resistance of the pest or otherfactors may require that the active ingredient be used at higher rates.The optimum rate depends usually upon a number of factors, for example,the type of pest being controlled, the type or the growth stage of theinfested plant, the row spacing or also the method of application. Morepreferably an effective rate range of the active arylpyrazole is fromabout 50 g/ha to about 400 g/ha.

When a pest is soil-borne, the active arylpyrazole generally in aformulated composition, is distributed evenly over the area to betreated (ie, for example broadcast or band treatment) in any convenientmanner and is applied at rates from about 5 to about 1 kg ai/ha,preferably from about 50 to about 250 g ai/ha. When applied as a rootdip to seedlings or drip irrigation to plants the liquid solution orsuspension contains from about 0.075 to about 1000 mg ai/l, preferablyfrom about 25 to about 200 mg ai/l. Application may be made, if desired,to the field or crop-growing area generally or in close proximity to theseed or plant to be protected from attack. The active component can bewashed into the soil by spraying with water over the area or can be leftto the natural action of rainfall. During or after application, theformulated arylpyrazole can, if desired, be distributed mechanically inthe soil, for example by ploughing, disking, or use of drag chains.Application can be prior to planting, at planting, after planting butbefore sprouting has taken place, or after sprouting.

The arylpyrazoles of the invention and methods of control of peststherewith are of particular value in the protection of field, forage,plantation, glasshouse, orchard or vineyard crops, of ornamentals, or ofplantation or forest trees, for example: cereals (such as wheat orrice), cotton, vegetables (such as peppers), field crops (such as sugarbeets, soybeans or oil seed rape), grassland or forage crops (such asmaize or sorghum), orchards or groves (such as of stone or pit fruit orcitrus), ornamental plants, flowers or vegetables or shrubs under glassor in gardens or parks, or forest trees (both deciduous and evergreen)in forests, plantations or nurseries.

They are also valuable in the protection of timber (standing, felled,converted, stored or structural) from attack, for example, by sawfliesor beetles or termites.

They have applications in the protection of stored products such asgrains, fruits, nuts, spices or tobacco, whether whole, milled orarylpyrazoleed into products, from moth, beetle, mite or grain weevilattack. Also protected are stored animal products such as skins, hair,wool or feathers in natural or converted form (e.g. as carpets ortextiles) from moth or beetle attack as well as stored meat, fish orgrains from beetle, mite or fly attack.

Additionally, the arylpyrazoles of the invention and methods of usethereof are of particular value in the control of arthropods, helminthsor protozoa which are injurious to, or spread or act as vectors ofdiseases domestic animals, for example those hereinbefore mentioned, andmore especially in the control of ticks, mites, lice, fleas, midges, orbiting, nuisance or myiasis flies. The arylpyrazoles of the inventionare particularly useful in controlling arthropods, helminths or protozoawhich are present inside domestic host animals or which feed in or onthe skin or suck the blood of the animal, for which purpose they may beadministered orally, parenterally, percutaneously or topically.

Furthermore, arylpyrazoles of the invention may be useful forcoccidiosis, a disease caused by infections from protozoan parasites ofthe genus Eimeria. It is an important potential cause of economic lossin domestic animals and birds, particularly those raised or kept underintensive conditions. For example, cattle, sheep, pigs or rabbits may beaffected, but the disease is especially important in poultry,particularly in chickens. Administration of a small amount of aarylpyrazole of the invention, preferably by a combination with feed iseffective in preventing or greatly reducing the incidence ofcoccidiosis. The arylpyrazoles are effective against both the cecal formand the intestinal forms. Furthermore, the arylpyrazoles of theinvention may also exert an inhibiting effect on oocytes by greatlyreducing the number and sporulation of those produced. The poultrydisease is generally spread by the birds picking up the infectiousorganism in droppings in or on contaminated litter, ground, food, ordrinking water. The disease is manifested by hemorrhage, accumulation ofblood in the ceca, passage of blood to the droppings, weakness anddigestive disturbances. The disease often terminates in the death of theanimal, but the fowl which survive severe infections have had theirmarket value subtantially reduced as a result of the infection.

The compositions hereinafter described for application to growing cropsor crop growing loci or as a seed dressing may, in general,alternatively be employed for topical application to animals or in theprotection of stored products, household goods, property or areas of thegeneral environment. Suitable means of applying the arylpyrazoles of theinvention include:

to growing crops as foliar sprays, dusts, granules, fogs or foams oralso as suspensions of finely divided or encapsulated compositions assoil or root treatments by liquid drenches, dusts, granules, smokes orfoams; to seeds of crops via application as seed dressings by liquidslurries or dusts;

to animals infested by or exposed to infestation by arthropods,helminths or protozoa, by parenteral, oral or topical application ofcompositions in which the active ingredient exhibits an immediate and/orprolonged action over a period of time against the arthropods, helminthsor protozoa, for example by incorporation in feed or suitableorally-ingestible pharmaceutical formulations, edible baits, salt licks,dietary supplements, pour-on formulations, sprays, baths, dips, showers,jets, dusts, greases, shampoos, creams, wax smears or livestockself-treatment systems;

to the environment in general or to specific locations where pests maylurk, including stored products, timber, household goods, or domestic orindustrial premises, as sprays, fogs, dusts, smokes, wax-smears,lacquers, granules or baits, or in tricklefeeds to waterways, wells,reservoirs or other running or standing water;

to domestic animals in feed to control fly larvae feeding in theirfeces;

In practice, the arylpyrazoles of the invention most frequently formparts of compositions. These compositions can be employed to control:arthopods, especially insects or mites; nematodes; or helminth orprotozoan pests. The compositions may be of any type known in the artsuitable for application to the desired pest in any premises or indooror outdoor area or by internal or external administration tovertebrates. These compositions contain at least one arylpyrazole offormula (I) or a pesticidally acceptable salt thereof, such as describedearlier, as the active ingredient in combination or association with oneor more other compatible components which are for example, solid orliquid carriers or diluents, adjuvants, surface-active-agents, or thelike appropriate for the intended use and which are agronomically ormedicinally acceptable. These compositions, which may be prepared by anymanner known in the art, likewise form a part of this invention.

These compositions may also contain other kinds of ingredients such asprotective colloids, adhesives, thickeners, thixotropic agents,penetrating agents, spray oils (especially for acaridical use),stabilizers, preservative agents (especially mold preservatives),sequestering agents, or the like, as well as other known activeingredients with pesticidal properties (particularly insecticidal,miticidal, nematicidal, or fungicidal) or with properties regulating thegrowth of plants. More generally, the arylpyrazoles employed in theinvention may be combined with all the solid or liquid additivescorresponding to the usual techniques of formulation.

Compositions, suitable for applications in agriculture, horticulture, orthe like include formulations suitable for use as, for example, sprays,dusts, granules, fogs, foams, emulsions, or the like.

The effective use doses of the arylpyrazoles employed in the inventioncan vary within wide limits, particularly depending on the nature of thepest to be eliminated or degree of infestation, for example, of cropswith these pests. In general, the compositions according to theinvention usually contain about 0.05 to about 95% (by weight) of one ormore active ingredients according to the invention, about 1 to about 95%of one or more solid or liquid carriers and, optionally, about 0.1 toabout 50% of one or more other compatible components, such assurface-active agents or the like.

In the present account, the term “carrier” denotes an organic orinorganic ingredient, natural or synthetic, with which the activeingredient is combined to facilitate its application, for example, tothe plant, to seeds or to the soil. This carrier is therefore generallyinert and it must be acceptable (for example, agronomically acceptable,particularly to the treated plant).

The carrier may be a solid, for example, clays, natural or syntheticsilicates, silica, resins, waxes, solid fertilizers (for exampleammonium salts), ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceousearth, or ground synthetic minerals, such as silica, alumina, orsilicates especially aluminium or magnesium silicates. As solid carriersfor granules the following are suitable: crushed or fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite; syntheticgranules of inorganic or organic meals; granules of organic materialsuch as sawdust, coconut shells, corn cobs, corn husks or tobaccostalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbentcarbon black; water soluble polymers, resins, waxes; or solidfertilizers. Such solid compositions may, if desired, contain one ormore compatible wetting, dispersing, emulsifying or colouring agentswhich, when solid, may also serve as a diluent.

The carrier may also be liquid, for example: water; alcohols,particularly butanol or glycol, as well as their ethers or esters,particularly methylglycol acetate; ketones, particularly acetone,cyclohexanone, methylethyl ketone, methylisobutylketone, or isophorone;petroleum fractions such as paraffinic or aromatic hydrocarbons,particularly xylenes or alkyl naphthalenes; mineral or vegetable oils;aliphatic chlorinated hydrocarbons, particularly trichioroethane ormethylene chloride; aromatic chlorinated hydrocarbons, particularlychlorobenzenes; water-soluble or strongly polar solvents such asdimethylformamide, dimethyl sulphoxide, or N-methylpyrrolidone;liquefied gases; or the like or a mixture thereof.

The surface-active agent may be an emulsifying agent, dispersing agentor wetting agent of the ionic or non-ionic type or a mixture of suchsurface-active agents. Amongst these are e.g., salts of polyacrylicacids, salts of lignosulphonic acids, salts of phenolsulphonic ornaphthalenesulphonic acids, polycondensates of ethylene oxide with fattyalcohols or fatty acids or fatty esters or fatty amines, substitutedphenols (particularly alkylphenols or arylphenols), salts ofsulphosuccinic acid esters, taurine derivatives (particularlyalkyltaurates), phosphoric esters of alcohols or of polycondensates ofethylene oxide with phenols, esters of fatty acids with polyols, orsulphate, sulphonate or phosphate functional derivatives of the abovearylpyrazoles. The presence of at least one surface-active agent isgenerally essential when the active ingredient and/or the inert carrierare only slightly water soluble or are not water soluble and the carrieragent of the composition for application is water.

Compositions of the invention may further contain other additives suchas adhesives or colorants. Adhesives such as carboxymethylcellulose ornatural or synthetic polymers in the form of powders, granules orlattices, such as arabic gum, polyvinyl alcohol or polyvinyl acetate,natural phospholipids, such as cephalins or lecithins, or syntheticphospholipids can be used in the formulations. It is possible to usecolorants such as inorganic pigments, for example: iron oxides, titaniumoxides or Prussian Blue; organic dyestuffs, such as alizarin dyestuffs,azo dyestuffs or metal phthalocyanine dyestuffs; or trace nutrients suchas salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

Compositions containing arylpyrazoles of formula (I), or pesticidallyacceptable salts thereof, which may be applied to control arthropod,plant nematode, helminth or protozoan pests, may also contain synergists(e.g. piperonyl butoxide or sesamex), stabilizing substances, otherinsecticides, acaricides, plant nematocides, anthelmintics oranticoccidials, fungicides (agricultural or veterinary as appropriate,e.g. benomyl and iprodione), bactericides, arthropod or vertebrateattractants or repellents or pheromones, deodorants, flavouring agents,dyes, or auxiliary therapeutic agents, e.g. trace elements. These may bedesigned to improve potency, persistence, safety, uptake where desired,spectrum of pests controlled or to enable the composition to performother useful functions in the same animal or area treated.

Examples of other pesticidally-active arylpyrazoles which may beincluded in, or used in conjunction with the compositions of the presentinvention are: acephate, chlorpyrifos, demeton-S-methyl, disulfoton,ethoprofos, fenitrothion, fenamiphos, fonofos, isazophos, isofenphos,malathion, monocrotophos, parathion, phorate, phosalone,pirimiphos-methyl, terbufos, triazophos, cyfluthrin, cypermethrin,deltamethrin, fenpropathrin, fenvalerate, permethrin, tefluthrin,aldicarb, carbosulfan, methomyl, oxamyl, pirimicarb, bendiocarb,teflubenzuron, dicofol, endosulfan, lindane, benzoximate, cartap,cyhexatin, tetradifon, avermectins, ivermectins, milbemycins,thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole.

For their agricultural application, the arylpyrazoles of the formula(I), or pesticidally acceptable salts thereof, are therefore generallyin the form of compositions, which are in various solid or liquid forms.

Solid forms of compositions which can be used are dusting powders (witha content of the arylpyrazole of formula (I), or a pesticidallyacceptable salt thereof, ranging up to 80%), wettable powders orgranules (including water dispersible granules), particularly thoseobtained by extrusion, compacting, impregnation of a granular carrier,or granulation starting from a powder (the content of the arylpyrazoleof formula (I), or a pesticidally acceptable salt thereof, in thesewettable powders or granules being between about 0.5 and about 80%).Solid homogenous or heterogenous compositions containing one or morearylpyrazoles of formula (I), or pesticidally acceptable salts thereof,for example granules, pellets, briquettes or capsules, may be used totreat standing or running water over a period of time. A similar effectmay be achieved using trickle or intermittent feeds of water dispersibleconcentrates as described herein.

Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions, or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

Liquid compositions, for example, in the form of emulsifiable or solubleconcentrates most frequently comprise about 5 to about 80% by weight ofthe active ingredient, while the emulsions or solutions which are readyfor application contain, in their case, about 0.01 to about 20% of theactive ingredient. Besides the solvent, the emulsifiable or solubleconcentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilizers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, for example, to plants, may be obtained from theseconcentrates by dilution with water. These compositions are includedwithin the scope of the compositions which may be employed in thepresent invention. The emulsions may be in the form of water-in-oil oroil-in-water type and they may have a thick consistency.

The liquid compositions of this invention may, in addition to normalagricultural use applications be used for example to treat substrates orsites infested or liable to infestation by arthropods (or other pestscontrolled by arylpyrazoles of this invention) including premises,outdoor or indoor storage or processing areas, containers or equipmentor standing or running water.

All these aqueous dispersions or emulsions or spraying mixtures can beapplied, for example, to crops by any suitable means, chiefly byspraying, at rates which are generally of the order of about 100 toabout 1,200 liters of spraying mixture per hectare, but may be higher orlower (eg. low or ultra-low volume) depending upon the need orapplication technique. The arylpyrazoles or compositions according tothe invention are conveniently applied to vegetation and in particularto roots or leaves having pests to be eliminated. Another method ofapplication of the arylpyrazoles or compositions according to theinvention is by chemigation, that is to say, the addition of aformulation containing the active ingredient to irrigation water. Thisirrigation may be sprinkler irrigation for foliar pesticides or it canbe ground irrigation or underground irrigation for soil or for systemicpesticides.

The concentrated suspensions, which can be applied by spraying, areprepared so as to produce a stable fluid product which does not settle(fine grinding) and usually contain from about 10 to about 75% by weightof active ingredient, from about 0.5 to about 30% of surface-activeagents, from about 0.1 to about 10% of thixotropic agents, from about 0to about 30% of suitable additives, such as anti-foaming agents,corrosion inhibitors, stabilizers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

The wettable powers (or powder for spraying) are usually prepared sothat they contain from about 10 to about 80% by weight of activeingredient, from about 20 to about 90% of a solid carrier, from about 0to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilizers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient(s) is(are) thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is(are) ground using a mill or other suitablegrinder. This produces wettable powders, the wettability and thesuspendability of which are advantageous. They may be suspended in waterto give any desired concentration and this suspension can be employedvery advantageously in particular for application to plant foliage.

The “water dispersible granules (WG)” (granules which are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. 1 to 20% by weight, or with an aqueous solution of adispersing agent or binder, followed by drying and screening), or by adry route (compacting followed by grinding and screening).

The rates and concentrations of the formulated compositions may varyaccording to the method of application or the nature of the compositionsor use thereof. Generally speaking, the compositions for application tocontrol arthropod, plant nematode, helminth or protozoan pests usuallycontain from about 0.00001% to about 95%, more particularly from about0.0005% to about 50% by weight of one or more arylpyrazoles of formula(I), or pesticidally acceptable salts thereof, or of total activeingredients (that is to say the arylpyrazole of formula (I), or apesticidally acceptable salt thereof, together with: other substancestoxic to arthropods or plant nematodes, anthelmintics, anticoccidials,synergists, trace elements or stabilizers). The actual compositionsemployed and their rate of application will be selected to achieve thedesired effect(s) by the farmer, livestock producer, medical orveterinary practitioner, pest control operator or other person skilledin the art.

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more arylpyrazoles of formula (I) or pesticidallyacceptable salts thereof. For administration to animals orally orparenterally, including percutaneously solid or liquid compositions,these normally contain from about 0. 1% to about 90% by weight of one ormore arylpyrazoles of formula (I) or pesticidally acceptable saltsthereof. Medicated feedstuffs normally contain from about 0.001% toabout 3% by weight of one or more arylpyrazoles of formula (I) orpesticidally acceptable salts thereof. Concentrates or supplements formixing with feedstuffs normally contain from about 5% to about 90%,preferably from about 5% to about 50%, by weight of one or morearylpyrazoles of formula (I) or pesticidally acceptable salts thereof.Mineral salt licks normally contain from about 0.1% to about 10% byweight of one or more arylpyrazoles of formula (I) or pesticidallyacceptable salts thereof.

Dusts or liquid compositions for application to livestock, goods,premises or outdoor areas may contain from about 0.0001% to about 15%,more especially from about 0.005% to about 2.0%, by weight, of one ormore arylpyrazoles of formula (I) or pesticidally acceptable saltsthereof. Suitable concentrations in treated waters are between about0.0001 ppm and about 20 ppm, more particularly about 0.001 ppm to about5.0 ppm. of one or more arylpyrazoles of formula (I), or pesticidallyacceptable salts thereof, and may be used therapeutically in fishfarming with appropriate exposure times. Edible baits may contain fromabout 0.01% to about 5%, preferably from about 0.01% to about 1.0%, byweight, of one or more arylpyrazoles of formula (I) or pesticidallyacceptable salts thereof.

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of arylpyrazoles of formula (I), orpesticidally acceptable salts thereof, will depend upon the species,age, or health of the vertebrate and upon the nature and degree of itsactual or potential infestation by arthropod, helminth or protozoanpests. A single dose of about 0.1 to about 100 mg, preferably about 2.0to about 20.0 mg, per kg body weight of the animal or doses of about0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, per kg bodyweight of the animal per day, for sustained medication, are generallysuitable by oral or parenteral administration. By use of sustainedrelease formulations or devices, the daily doses required over a periodof months may be combined and administered to animals on a singleoccasion.

The following composition EXAMPLES 2A-2M illustrate compositions for useagainst arthropods, especially mites or insects, plant nematodes, orhelminth or protozoan pests which comprise, as active ingredient,arylpyrazoles of formula (I), or pesticidally acceptable salts thereof,such as those described in preparative examples. The compositionsdescribed in EXAMPLES 2A-2M can each be diluted to give a sprayablecompositon at concentrations suitable for use in the field. Genericchemical descriptions of the ingredients (for which all of the followingpercentages are in weight percent), used in the composition EXAMPLES2A-2M exemplified below, are as follows:

Trade Name Chemical Description Ethylan BCP Nonylphenol ethylene oxidecondensate Soprophor BSU Tristyrylphenol ethylene oxide condensateArylan CA A 70% w/v solution of calcium dodecylbenzenesulfonate Solvesso150 Light C₁₀ aromatic solvent Arylan S Sodium dodecylbenzenesulfonateDarvan No2 Sodium lignosulphonate Celite PF Synthetic magnesium silicatecarrier Sopropon T36 Sodium salts of polycarboxylic acids Rhodigel 23Polysaccharide xanthan gum Bentone 38 Organic derivative of magnesiummontmorillonite Aerosil Microfine silicon dioxide

EXAMPLE 2A

A water soluble concentrate is prepared with the composition as follows:

Active ingredient 7% Ethylan BCP 10% N-methylpyrrolidone 83%

To a solution of Ethylan BCP dissolved in a portion ofN-methylpyrrolidone is added the active ingredient with heating andstirring until dissolved. The resulting solution is made up to volumewith the remainder of the solvent.

EXAMPLE 2B

An emulsifiable concentrate (EC) is prepared with the composition asfollows:

Active ingredient 25%(max) Soprophor BSU 10% Arylan CA  5%N-methylpyrrolidone 50% Solvesso 150 10%

The first three components are dissolved in N-methylpyrrolidone and tothis is then added the Solvesso 150 to give the final volume.

EXAMPLE 2C

A wettable powder (WP) is prepared with the composition as follows:

Active ingredient 40% Arylan S 2% Darvan No2 5% Celite PF 53%

The ingredients are mixed and ground in a hammer-mill to a powder with aparticle size of less than 50 microns.

EXAMPLE 2D

An aqueous-flowable formulation is prepared with the composition asfollows:

Active ingredient 40.00% Ethylan BCP 1.00% Sopropon T360. 0.20% Ethyleneglycol 5.00% Rhodigel 230. 0.15% Water 53.65%

The ingredients are intimately mixed and are ground in a bead mill untila mean particle size of less than 3 microns is obtained.

EXAMPLE 2E

An emulsifiable suspension concentrate is prepared with the compositionas follows:

Active ingredient 30.0% Ethylan BCP 10.0% Bentone 38 0.5% Solvesso 15059.5%

The ingredients are intimately mixed and ground in a beadmill until amean particle size of less than 3 microns is obtained.

EXAMPLE 2F

A water dispersible granule is prepared with the composition as follows:

Active ingredient 30% Darvan No 2 15% Arylan S  8% Celite PF 47%

The ingredients are mixed, micronized in a fluid-energy mill and thengranulated in a rotating pelletizer by spraying with water (up to 10%).The resulting granules are dried in a fluid-bed drier to remove excesswater.

EXAMPLE 2G

A dusting powder is prepared with the composition as follows:

Active ingredient  1 to 10% Talc powder-superfine 99 to 90%

The ingredients are intimately mixed and further ground as necessary toachieve a fine powder. This powder may be appplied to a locus ofarthropod infestation, for example refuse dumps, stored products orhousehold goods or animals infested by, or at risk of infestation by,arthropods to control the arthropods by oral ingestion. Suitable meansfor distributing the dusting powder to the locus of arthropodinfestation include mechanical blowers, handshakers or livestock selftreatment devices.

EXAMPLE 2H

An edible bait is prepared with the composition as follows:

Active ingredient 0.1 to 1.0% Wheat flour 80% Molasses 19.9 to 19%  

The ingredients are intimately mixed and formed as required into a baitform. This edible bait may be distributed at a locus, for exampledomestic or industrial premises, e.g. kitchens, hospitals or stores, oroutdoor areas, infested by arthropods, for example ants, locusts,cockroaches or flies, to control the arthropods by oral ingestion.

EXAMPLE 2I

A solution formulation is prepared with a composition as follows:

Active ingredient 15% Dimethyl sulfoxide 85%

The active ingredient is dissolved in dimethyl sulfoxide with mixing andor heating as required. This solution may be applied percutaneously as apour-on application to domestic animals infested by arthropods or, aftersterilization by filtration through a polytetrafluoroethylene membrane(0.22 micrometer pore size), by parenteral injection, at a rate ofapplication of from 1.2 to 12 ml of solution per 100 kg of animal bodyweight.

EXAMPLE 2J

A wettable powder is prepared with the composition as follows:

Active ingredient 50% Ethylan BCP 5% Aerosil 5% Celite PF 40%

The Ethylan BCP is absorbed onto the Aerosil which is then mixed withthe other ingredients and ground in a hammer-mill to give a wettablepowder, which may be diluted with water to a concentration of from0.001% to 2% by weight of the active arylpyrazole and applied to a locusof infestation by arthropods, for example, dipterous larvae or plantnematodes, by spraying, or to domestic animals infested by, or at riskof infection by arthropods, helminths or protozoa, by spraying ordipping, or by oral administration in drinking water, to control thearthropods, helminths or protozoa.

EXAMPLE 2K

A slow release bolus composition is formed from granules containing thefollowing components in varying percentages(similar to those describedfor the previous compositions) depending upon need:

Active ingredient

Density agent

Slow-release agent

Binder

The intimately mixed ingredients are formed into granules which arecompressed into a bolus with a specific gravity of 2 or more. This canbe administered orally to ruminant domestic animals for retention withinthe reticulo-rumen to give a continual slow release of activearylpyrazole over an extended period of time to control infestation ofthe ruminant domestic animals by arthropods, helminths or protozoa.

EXAMPLE 2L

A slow release composition in the form of granules, pellets, brickettesor the like can be prepared with compositions as follows:

Active ingredient 0.5 to 25% Polyvinyl chloride  75 to 99.5% Dioctylphthalate (plasticizer)

The components are blended and then formed into suitable shapes bymelt-extrusion or molding. These composition are useful, for example,for addition to standing water or for fabrication into collars oreartags for attachment to domestic animals to control pests by slowrelease.

EXAMPLE 2M

A water dispersible granule is prepared with the composition as follows:

Active ingredient 85% (max) Polyvinylpyrrolidone 5% Attapulgite clay 6%Sodium lauryl sulfate 2% Glycerine 2%

The ingredients are mixed as a 45% slurry with water and wet milled to aparticle size of 4 microns, then spray-dried to remove water.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions and changes can be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A compound of formula (I):

wherein: A is selected from:

X is —NR₁₇; R₁ is hydrogen, substituted or unsubstituted alkyl or a lonepair of electrons; R₂ is —S(O)_(n)R₁₈ or R₁₉; R₃ is hydrogen, halogen,—C(O)R₂₀, —S(O)_(p)R₂₁, alkyl, haloalkyl, —OR₂₂, —N═C(R₂₃)(R₂₄),alkenyl, —NR₂₅R₂₆, 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, or —CH═NOH; R₄, R₅and R₇ are independently selected from hydrogen, halogen and alkyl; R₆is halogen, haloalkyl, haloalkoxy, —S(O)_(q)R₂₇ or SF₅; R₁₀, R₁₁, R₁₂and R₁₃ are independently selected from hydrogen, hydroxy, C(O)R₃₂,alkyl and haloalkyl; or R₁₀ and R₁₁ can together form a carbonylradical; or R₁₂ and R₁₃ can together form a carbonyl radical; R₁₄ andR₁₅ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl, —OR₂₈, —NR₂₉R₃₀,—S(O)_(m)R₃₁, —C(O)R₃₂, cyano and nitro; or R₁₄ and R₁₅ can togetherwith the carbons to which they are attached form a cyclic divalentalkylene radical which may be interrupted by one or more heteroatoms;R₁₇ is hydrogen, substituted or unsubstituted alkyl or a lone pair ofelectrons; R₁₈ is alkyl, alkenyl, alkynyl, or C₃-C₆ cycloalkyl, each ofwhich is optionally substituted by one or more halogen; R₁₉ is alkyl orhaloalkyl; R₂₀ is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy; R₂₁is alkyl, haloalkyl, or aryl; R₂₂ and R₂₃ are independently selectedfrom hydrogen, alkyl and haloalkyl; R₂₄ is alkyl, haloalkyl, alkoxy orphenyl each of which is optionally substituted by one or more groupsselected from hydroxy, halogen, alkoxy, —CN, alkyl and —S(O)_(r)-alkyl;R₂₅ and R₂₆ are independently selected from hydrogen, NH₂, —S(O)_(r)R₃₄,—C(O)R₃₅, substituted or unsubstituted alkyl, and substituted orunsubstituted alkenyl and alkynyl; or R₂₅ and R₂₆ may form together adivalent alkylene radical which may be interrupted by one or moreheteroatoms; R₂₇ is haloalkyl; R₃₂ is selected from hydrogen,substituted or unsubstituted alkyl, substituted or unsubstituted aryl,hydroxy, alkoxy, and substituted or unsubstituted amino; R₃₄ issubstituted or unsubstituted alkyl; R₃₅ is hydrogen, alkyl, haloalkyl,aryl; alkenyl; —OR₃₆, —SR₃₇, or —NR₃₈R₃₉; R₃₆ and R₃₇ are independentlyselected from hydrogen, alkyl, haloalkyl and aryl; R₃₈ and R₃₉ areindependently selected from hydrogen, alkyl, haloalkyl and aryl; n, p, qand r independently represent zero, one or two; M is C-halo, C—CH₃,C—CH₂F, C—CH₂Cl, C—NO₂, or N; or a pesticidally acceptable salt thereof;provided that: when A is (G5), R₁ and R₁₇ represent lone pairs ofelectrons; when A is (G2), R₁₀ and R₁₁ are not simultaneously hydroxy;when A is (G2), R₁₂ and R₁₃ are not simultaneously hydroxy.
 2. Anarylpyrazole of formula (I) according to claim 1 wherein R₁ is hydrogenor a lone pair of electrons.
 3. An arylpyrazole of formula (I) accordingto claim 1 wherein: A is (G2); R₁ is H or alkyl; X is —NH—; R₁₀, R₁₁,R₁₂ and R₁₃ are selected from hydrogen, —OH, and —C(O)R₃₂; R₂ is—S(O)_(n)R₁₈; R₃ is —NR₂₅R₂₆; R₄ is halogen; R₅ and R₇ are hydrogen; R₆is haloalkyl; R₁₈ is alkyl; R₂₅ and R₂₆ are independently selected fromhydrogen and alkyl; and R₃₂ is alkoxy or amino.
 4. An arylpyrazole offormula (I) according to claim 1 wherein the aryl groups comprising theR₄ to R₇ and M radicals in formula (I) are:2,6-dichloro-4-trifluoromethylphenyl;2,6-dichloro-4-trifluoromethoxyphenyl;2-bromo-6-chloro-4-trifluoromethylphenyl;2-bromo-6-chloro-4-trifluoromethoxyphenyl;2,6-difluoro-4-trifluoromethylphenyl; 2-chloro-4-trifluoromethylphenyl;3-chloro-5-trifluoromethyl-2-pyridinyl;3-chloro-5-trifluoromethoxy-2-pyridinyl;2-bromo-6-fluoro-4-difluoromethylphenyl;2-chloro-6-fluoro-4-trifluoromethylphenyl;2,6-dibromo-4-trifluoromethylphenyl;2,6-dibromo-4-trifluoromethoxyphenyl; and2,6-dichloro-4-pentafluorothiophenyl.
 5. An arylpyrazole of formula (I)according to claim 1 wherein R₃ is NH₂; R₄ is Cl; M is C—Cl; R₅═R₆═H; R₆is CF₃ and A is G5, R₁ and R₁₇ are lone pairs of electrons, R₁₄ and R₁₅are H and R₂ is SOCH₃.
 6. A pesticidal composition comprising: (a) anarylpyrazole of formula (I):

 wherein: A is selected from:

X is —NR₁₇; R₁ is hydrogen, substituted or unsubstituted alkyl or a lonepair of electrons; R₂ is —S(O)_(n)R₁₈ or R₁₉; R₃ is hydrogen, halogen,—C(O)R₂₀, —S(O)_(p)R₂₁, alkyl, haloalkyl, —OR₂₂, —N═C(R₂₃)(R₂₄),alkenyl, —NR₂₅R₂₆, 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, or —CH═NOH; R₄, R₅and R₇ are independently selected from hydrogen, halogen and alkyl; R₆is halogen, haloalkyl, haloalkoxy, —S(O)_(q)R₂₇ or SF₅; R₁₀, R₁₁, R₁₂and R₁₃ are independently selected from hydrogen, hydroxy, C(O)R₃₂,alkyl and haloalkyl; or R₁₀ and R₁₁ can together form a carbonylradical; or R₁₂ and R₁₃ can together form a carbonyl radical; R₁₄ andR₁₅ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl, —OR₂₈, —NR₂₉R₃₀,—S(O)_(m)R₃₁, —C(O)R₃₂, cyano and nitro; or R₁₄ and R₁₅ can togetherwith the carbons to which they are attached form a cyclic divalentalkylene radical which may be interrupted by one or more heteroatoms;R₁₇ is hydrogen, substituted or unsubstituted alkyl or a lone pair ofelectrons; R₁₈ is alkyl, alkenyl, alkynyl, or C₃-C₆ cycloalkyl, each ofwhich is optionally substituted by one or more halogen; R₁₉ is alkyl orhaloalkyl; R₂₀ is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy; R₂₁is alkyl, haloalkyl, or aryl; R₂₂ and R₂₃ are independently selectedfrom hydrogen, alkyl and haloalkyl; R₂₄ is alkyl, haloalkyl, alkoxy orphenyl each of which is optionally substituted by one or more groupsselected from hydroxy, halogen, alkoxy, —CN, alkyl, and —S(O)_(r)-alkyl;R₂₅ and R₂₆ are independently selected from hydrogen, NH₂, —S(O)_(r)R₃₄,—(O)R₃₅, substituted or unsubstituted alkyl, and substituted orunsubstituted alkenyl and alkynyl; or R₂₅ and R₂₆ may form together adivalent alkylene radical which may be interrupted by one or moreheteroatoms; R₂₇ is haloalkyl; R₃₂ is selected from hydrogen,substituted or unsubstituted alkyl, substituted or unsubstituted aryl,hydroxy, alkoxy, and substituted or unsubstituted amino; R₃₄ issubstituted or unsubstituted alkyl; R₃₅ is hydrogen, alkyl, haloalkyl,aryl; alkenyl; —OR₃₆, —SR₃₇, or —NR₃₈R₃₉; R₃₆ and R₃₇ are independentlyselected from hydrogen, alkyl, haloalkyl and aryl; R₃₈ and R₃₉ areindependently selected from hydrogen, alkyl, haloalkyl and aryl; n, p, qand r independently represent zero, one or two; M is C-halo, C—CH₃,C—CH₂F, C—CH₂Cl, C—NO₂, or N; or a pesticidally acceptable salt thereof;provided that: when A is (G5), R₁ and R₁₇ represent lone pairs ofelectrons; when A is (G2), R₁₀ and R₁₁ are not simultaneously hydroxy;when A is (G2), R₁₂ and R₁₃ are not simultaneously hydroxy; and (b) apesticidally acceptable carrier therefor.
 7. A composition according toclaim 6 which has from about 0.05 to about 95% (by weight) of anarylpyrazole of formula (I).
 8. A pesticidal composition according toclaim 6 which has from about 0.00005 to about 90% (by weight) of anarylpyrazole of formula (I).
 9. A method for the control of pests at alocus comprising applying to the said locus a pesticidally effectiveamount of an arylpyrazole of formula (I):

wherein: A is selected from:

X is —NR₁₇; R₁ is hydrogen, substituted or unsubstituted alkyl or a lonepair of electrons; R₂ is —S(O)_(n)R₁₈ or R₁₉; R₃ is hydrogen, halogen,—C(O)R₂₀, —S(O)_(p)R₂₁, alkyl, haloalkyl, —OR₂₂, —N═C(R₂₃)(R₂₄),alkenyl, —NR₂₅R₂₆, 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, or —CH═NOH; R₄, R₅and R₇ are independently selected from hydrogen, halogen and alkyl; R₆is halogen, haloalkyl, haloalkoxy, —S(O)_(q)R₂₇ or SF₅; R₁₀, R₁₁, R₁₂and R₁₃ are independently selected from hydrogen, hydroxy, C(O)R₃₂,alkyl and haloalkyl; or R₁₀ and R₁₁ can together form a carbonylradical; or R₁₂ and R₁₃ can together form a carbonyl radical; R₁₄ andR₁₅ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl, —OR₂₈, —NR₂₉R₃₀,—S(O)_(m)R₃₁, —C(O)R₃₂, cyano and nitro; or R₁₄ and R₁₅ can togetherwith the carbons to which they are attached form a cyclic divalentalkylene radical which may be interrupted by one or more heteroatoms;R₁₇ is hydrogen, substituted or unsubstituted alkyl or a lone pair ofelectrons; R₁₈ is alkyl, alkenyl, alkynyl, or C₃-C₆ cycloalkyl, each ofwhich is optionally substituted by one or more halogen; R₁₉ is alkyl orhaloalkyl; R₂₀ is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy; R₂₁is alkyl, haloalkyl, or aryl; R₂₂ and R₂₃ are independently selectedfrom hydrogen, alkyl and haloalkyl; R₂₄ is alkyl, haloalkyl, alkoxy orphenyl each of which is optionally substituted by one or more groupsselected from hydroxy, halogen, alkoxy, —CN, alkyl and —S(O)_(r)-alkyl;R₂₅ and R₂₆ are independently selected from hydrogen, NH₂, —S(O)_(r)R₃₄,—C(O)R₃₅, substituted or unsubstituted alkyl, and substituted orunsubstituted alkenyl and alkynyl; or R₂₅ and R₂₆ may form together adivalent alkylene radical which may be interrupted by one or moreheteroatoms; R₂₇ is haloalkyl; R₃₂ is selected from hydrogen,substituted or unsubstituted alkyl, substituted or unsubstituted aryl,hydroxy, alkoxy, and substituted or unsubstituted amino; R₃₄ issubstituted or unsubstituted alkyl; R₃₅ is hydrogen, alkyl, haloalkyl,aryl; alkenyl; —OR₃₆, —SR₃₇, or —NR₃₈R₃₉; R₃₆ and R₃₇ are independentlyselected from hydrogen, alkyl, haloalkyl and aryl; R₃₈ and R₃₉ areindependently selected from hydrogen, alkyl, haloalkyl and aryl; n, p, qand r independently represent zero, one or two; M is C-halo, C—CH₃,C—CH₂F, C—CH₂Cl, C—NO₂, or N; or a pesticidally acceptable salt thereof;provided that: when A is (G5), R₁ and R₁₇ represent lone pairs ofelectrons; when A is (G2), R₁₀ and R₁₁ are not simultaneously hydroxy;when A is (G2), R₁₂ and R₁₃ are not simultaneously hydroxy.
 10. Themethod according to claim 9 wherein the pests are insects.
 11. Themethod according to claim 10 wherein the insects are sucking insects.12. The method according to claim 9 wherein the locus is a crop area.13. The method according to claim 9 wherein the arylpyrazole is appliedat a locus at a rate of from 5 g to about 1 kg/ha.
 14. The methodaccording to claim 9, wherein said locus is an animal.
 15. The methodaccording to claim 14, wherein said compound is applied to said locus ata rate of from about 0.1 to 20 mg per kg body weight of the animal perday.
 16. A process for preparing an arylpyrazole of formula (I)according to claim 1 which comprises reacting a compound of formula(II):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, and M are defined as in claim 1: a)in the case of A=G2, with an aldehyde or ketone of the formulaR₁₀C(O)C(O)R₁₃ wherein R₁₀ and R₁₃ are independently selected fromhydrogen and alkyl; or with a compound of the formula R₁₀R₁₁CLCLR₁₂R₁₃;wherein ‘L and L’ are leaving groups; and wherein R₁₀, R₁₁, R₁₂ and R₁₃are not hydroxy; or with a compound R₃₂C(O)CC(O)R₃₂ in the optionalpresence of a base; and b) in the case of A=G5, wherein X is NH and R₁₇is H, with a dicarbonyl compound of the formula R₁₄C(O)C(O)R₁₅.